Electron Microscopy Studies of Soft Nanomaterials.

This review highlights recent efforts on applying electron microscopy (EM) to soft (including biological) nanomaterials. We will show how developments of both the hardware and software of EM have enabled new insights into the formation, assembly, and functioning (e.g., energy conversion and storage, phonon/photon modulation) of these materials by providing shape, size, phase, structural, and chemical information at the nanometer or higher spatial resolution. Specifically, we first discuss standard real-space two-dimensional imaging and analytical techniques which are offered conveniently by microscopes without special holders or advanced beam technology. The discussion is then extended to recent advancements, including visualizing three-dimensional morphology of soft nanomaterials using electron tomography and its variations, identifying local structure and strain by electron diffraction, and recording motions and transformation by in situ EM. On these advancements, we cover state-of-the-art technologies designed for overcoming the technical barriers for EM to characterize soft materials as well as representative application examples. The even more recent integration of machine learning and its impacts on EM are also discussed in detail. With our perspectives of future opportunities offered at the end, we expect this review to inspire and stimulate more efforts in developing and utilizing EM-based characterization methods for soft nanomaterials at the atomic to nanometer length scales in academic research and industrial applications.

4D-STEM Mapping of Nanocrystal Reaction Dynamics and Heterogeneity in a Graphene Liquid Cell.

Chemical reaction kinetics at the nanoscale are intertwined with heterogeneity in structure and composition. However, mapping such heterogeneity in a liquid environment is extremely challenging. Here we integrate graphene liquid cell (GLC) transmission electron microscopy and four-dimensional scanning transmission electron microscopy to image the etching dynamics of gold nanorods in the reaction media. Critical to our experiment is the small liquid thickness in a GLC that allows the collection of high-quality electron diffraction patterns at low dose conditions. Machine learning-based data-mining of the diffraction patterns maps the three-dimensional nanocrystal orientation, groups spatial domains of various species in the GLC, and identifies newly generated nanocrystallites during reaction, offering a comprehensive understanding on the reaction mechanism inside a nanoenvironment. This work opens opportunities in probing the interplay of structural properties such as phase and strain with solution-phase reaction dynamics, which is important for applications in catalysis, energy storage, and self-assembly.

Controlling the Nucleation and Growth of Au on a-Se Nanospheres to Enhance Their Cellular Uptake and Cytotoxicity.

We report a method to experimentally control the heterogeneous nucleation and growth of Au nanoparticles on the surface of amorphous Se (a-Se) nanospheres. When a AuIII precursor is added into a colloidal suspension of a-Se nanospheres, galvanic replacement occurs between them and the resultant Au0 atoms then heterogeneously nucleate and grow from the surface of the a-Se nanospheres. As a unique feature of this system, the Au0 atoms can only be produced on the surface of the a-Se nanospheres in the nucleation stage. Once Au nuclei are formed on the surface at the very beginning of a synthesis, they will serve as the preferential sites for further deposition of Au0 atoms, making it possible to control the number of Au nanoparticles on each nanosphere and the morphology of the final product. The dependence of the initial reduction rate on the pH can be used to obtain Se-Au hybrid nanoparticles containing one, two, three, and multiple Au nanoparticles on the surface of each a-Se nanosphere. The presence of Au patches on the hybrid nanoparticles offers an experimental handle to optimize the ligand distribution for the achievement of enhanced cellular uptake and cytotoxicity for the a-Se nanospheres.

Noble-Metal Nanocrystals with Controlled Shapes for Catalytic and Electrocatalytic Applications.

The successful synthesis of noble-metal nanocrystals with controlled shapes offers many opportunities to not only maneuver their physicochemical properties but also optimize their figures of merit in a wide variety of applications. In particular, heterogeneous catalysis and surface science have benefited enormously from the availability of this new class of nanomaterials as the atomic structure presented on the surface of a nanocrystal is ultimately determined by its geometric shape. The immediate advantages may include significant enhancement in catalytic activity and/or selectivity and substantial reduction in materials cost while providing a well-defined model system for mechanistic study. With a focus on the monometallic system, this review article provides a comprehensive account of recent progress in the development of noble-metal nanocrystals with controlled shapes, in addition to their remarkable performance in a large number of catalytic and electrocatalytic reactions. We hope that this review article offers the impetus and roadmap for the development of next-generation catalysts vital to a broad range of industrial applications.

Phase-Controlled Synthesis of Ru Nanocrystals via Template-Directed Growth: Surface Energy versus Bulk Energy.

Despite the successful control of crystal phase using template-directed growth, much remains unknown about the underlying mechanisms. Here, we demonstrate that the crystal phase taken by the deposited metal depends on the lateral size of face-centered cubic (fcc)-Pd nanoplate templates with 12 nm plates giving fcc-Ru while 18-26 nm plates result in hexagonal closed-packed (hcp)-Ru. Although Ru overlayers with a metastable fcc- (high in bulk energy) or stable hcp-phase (low in bulk energy) can be epitaxially deposited on the basal planes, the lattice mismatch will lead to jagged hcp- (high in surface energy) and smooth fcc-facets (low in surface energy), respectively, on the side faces. As the proportion of basal and side faces on the nanoplates varies with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. The Pd@fcc-Ru outperforms the Pd@hcp-Ru nanoplates toward ethylene glycol and glycerol oxidation reactions.

Slowly Removing Surface Ligand by Aging Enhances the Stability of Pd Nanosheets toward Electron Beam Irradiation and Electrocatalysis.

Surface ligands play an important role in shape-controlled growth and stabilization of colloidal nanocrystals. Their quick removal tends to cause structural deformation and/or aggregation to the nanocrystals. Herein, we demonstrate that the surface ligand based on poly(vinylpyrrolidone) (PVP) can be slowly removed from Pd nanosheets (NSs, 0.93±0.17 nm in thickness) by simply aging the colloidal suspension. The aged Pd NSs show well-preserved morphology, together with significantly enhanced stability toward both e-beam irradiation and electrocatalysis (e.g., ethanol oxidation). It is revealed that the slow desorption of PVP during aging forces the re-exposed Pd atoms to reorganize, facilitating the surface to transform from being nearly perfect to defect-rich. The resultant Pd NSs with abundant defects no longer rely on surface ligand to stabilize the atomic arrangement and thus show excellent structural and electrochemical stability. This work provides a facile and effective method to maintain the integrity of colloidal nanocrystals by slowly removing the surface ligand.

Physical Transformations of Noble-Metal Nanocrystals upon Thermal Activation.

ConspectusThe last two decades have witnessed the successful development of noble-metal nanocrystals with well-controlled properties for a variety of applications in catalysis, plasmonics, electronics, and biomedicine. Most of these nanocrystals are kinetically controlled products greatly deviated from the equilibrium state defined by thermodynamics. When subjected to elevated temperatures, their arrangements of atoms are expected to undergo various physical transformations, inducing changes to the shape, morphology (hollow vs solid), spatial distribution of elements (segregated vs alloyed/intermetallic), internal structure (twinned vs single-crystal), and crystal phase. In order to optimize the performance of these nanocrystals in various applications, there is a pressing need to understand and improve their thermal stability.By integrating in situ heating with transmission electron microscopy or X-ray diffraction, we have investigated the physical transformations of various types of noble-metal nanocrystals in real time. We have also explored the atomistic detail responsible for a physical transformation using first-principles calculations, providing insightful guidance for the development of noble-metal nanocrystals with augmented thermal stability. Specifically, solid nanocrystals were observed to transform into pseudospherical particles favored by thermodynamics by reducing the surface area while eliminating the facets high in surface energy. For nanocrystals of relatively large in size, a single-crystal lattice was more favorable than a twinned structure. When switching to core-shell nanocrystals, the elevation in temperature caused changes to the elemental distribution in addition to shape transformation. The compositional stability of a core-shell nanocrystal was found to be strongly dependent on the shape and thus the type of facet expressed on the surface. For hollow nanocrystals such as nanocages and nanoframes, their thermal stabilities were typically inferior to the solid counterparts, albeit their unique structure and large specific surface area are highly desired in applications such as catalysis. When a metastable crystal structure was involved, phase transition was also observed at a temperature close to that responsible for shape or compositional change. We hope the principles, methodologies, and mechanistic insights presented in this Account will help the readers achieve a good understanding of the physical transformations that are expected to take place in noble-metal nanocrystals when they are subjected to thermal activation. Such an understanding may eventually lead to the development of effective methods for retarding or even preventing some of the transformations.

Twin-Directed Deposition of Pt on Pd Icosahedral Nanocrystals for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction.

Platinum nanocrystals featuring a multiply twinned structure and uniform sizes below 5 nm are superb catalytic materials, but it is difficult to synthesize such particles owing to the high twin-boundary energy (166 mJ/m2) of Pt. Here, we report a simple route to the synthesis of such nanocrystals by selectively growing them from the vertices of Pd icosahedral seeds. The success of this synthesis critically depends on the introduction of Br- ions to slow the reduction kinetics of the Pt(II) precursor while limiting the surface diffusion of Pt adatoms by conducting the synthesis at 30 °C. Owing to the small size and multiply twinned structure of Pt dots, the as-obtained Pd-Pt nanocrystals show remarkably enhanced activity and durability toward oxygen reduction, with a mass activity of 1.23 A mg-1Pt and a specific activity of 0.99 mA cm-2Pt, which are 8.2 and 4.5 times as high as those of the commercial Pt/C.

Bifunctional Janus Particles as Multivalent Synthetic Nanoparticle Antibodies (SNAbs) for Selective Depletion of Target Cells.

Monoclonal antibodies (mAb) have had a transformative impact on treating cancers and immune disorders. However, their use is limited by high development time and monetary cost, manufacturing complexities, suboptimal pharmacokinetics, and availability of disease-specific targets. To address some of these challenges, we developed an entirely synthetic, multivalent, Janus nanotherapeutic platform, called Synthetic Nanoparticle Antibodies (SNAbs). SNAbs, with phage-display-identified cell-targeting ligands on one "face" and Fc-mimicking ligands on the opposite "face", were synthesized using a custom, multistep, solid-phase chemistry method. SNAbs efficiently targeted and depleted myeloid-derived immune-suppressor cells (MDSCs) from mouse-tumor and rat-trauma models, ex vivo. Systemic injection of MDSC-targeting SNAbs efficiently depleted circulating MDSCs in a mouse triple-negative breast cancer model, enabling enhanced T cell and Natural Killer cell infiltration into tumors. Our results demonstrate that SNAbs are a versatile and effective functional alternative to mAbs, with advantages of a plug-and-play, cell-free manufacturing process, and high-throughput screening (HTS)-enabled library of potential targeting ligands.

Pt-Co@Pt Octahedral Nanocrystals: Enhancing Their Activity and Durability toward Oxygen Reduction with an Intermetallic Core and an Ultrathin Shell.

Despite extensive efforts devoted to the synthesis of Pt-Co bimetallic nanocrystals for fuel cell and related applications, it remains a challenge to simultaneously control atomic arrangements in the bulk and on the surface. Here we report a synthesis of Pt-Co@Pt octahedral nanocrystals that feature an intermetallic, face-centered tetragonal Pt-Co core and an ultrathin Pt shell, together with the dominance of {111} facets on the surface. When evaluated as a catalyst toward the oxygen reduction reaction (ORR), the nanocrystals delivered a mass activity of 2.82 A mg-1 and a specific activity of 9.16 mA cm-2, which were enhanced by 13.4 and 29.5 times, respectively, relative to the values of a commercial Pt/C catalyst. More significantly, the mass activity of the nanocrystals only dropped 21% after undergoing 30 000 cycles of accelerated durability test, promising an outstanding catalyst with optimal performance for ORR and related reactions.

Kinetically Controlled Synthesis of Rhodium Nanocrystals with Different Shapes and a Comparison Study of Their Thermal and Catalytic Properties.

We report the synthesis of Rh nanocrystals with different shapes by controlling the kinetics involved in the growth of preformed Rh cubic seeds. Specifically, Rh nanocrystals with cubic, cuboctahedral, and octahedral shapes can all be obtained from the same cubic seeds under suitable reduction kinetics for the precursor. The success of such a synthesis also relies on the use of a halide-free precursor to avoid oxidative etching, as well as the involvement of a sufficiently high temperature to remove Br- ions from the seeds while ensuring adequate surface diffusion. The availability of Rh nanocrystals with cubic and octahedral shapes allows for an evaluation of the facet dependences of their thermal and catalytic properties. The data from in situ electron microscopy studies indicate that the cubic and octahedral Rh nanocrystals can keep their original shapes up to 700 and 500 °C, respectively. When tested as catalysts for hydrazine decomposition, the octahedral nanocrystals exhibit almost 4-fold enhancement in terms of H2 selectivity relative to the cubic counterpart. As for ethanol oxidation, the order is reversed, with the cubic nanocrystals being about three times more active than the octahedral sample.

Kinetically Controlled Synthesis of Pd-Cu Janus Nanocrystals with Enriched Surface Structures and Enhanced Catalytic Activities toward CO2 Reduction.

Bimetallic nanocrystals often outperform their monometallic counterparts in catalysis as a result of the electronic coupling and geometric effect arising from two different metals. Here we report a facile synthesis of Pd-Cu Janus nanocrystals with controlled shapes through site-selected growth by reducing the Cu(II) precursor with glucose in the presence of hexadecylamine and Pd icosahedral seeds. Specifically, at a slow reduction rate, the Cu atoms nucleate and grow from one vertex of the icosahedral seed to form a penta-twinned Janus nanocrystal in the shape of a pentagonal bipyramid or decahedron. At a fast reduction rate, in contrast, the Cu atoms can directly nucleate from or diffuse to the edge of the icosahedral seed for the generation of a singly twinned Janus nanocrystal in the shape of a truncated bitetrahedron. The segregation of two elements and the presence of twin boundaries on the surface make the Pd-Cu Janus nanocrystals effective catalysts for the electrochemical reduction of CO2. An onset potential as low as -0.7 VRHE (RHE: reversible hydrogen electrode) was achieved for C2+ products in 0.5 M KHCO3 solution, together with a faradaic efficiency approaching 51.0% at -1.0 VRHE. Density functional theory and Pourbaix phase diagram studies demonstrated that the high CO coverage on the Pd sites (either metallic or hydride form) during electrocatalysis enabled the spillover of CO to the Cu sites toward subsequent C-C coupling, promoting the formation of C2+ species. This work offers insights for the rational fabrication of bimetallic nanocrystals featuring desired compositions, shapes, and twin structures for catalytic applications.

Using Reduction Kinetics to Control and Predict the Outcome of a Colloidal Synthesis of Noble-Metal Nanocrystals.

Improving the performance of noble-metal nanocrystals in various applications critically depends on our ability to manipulate their synthesis in a rational, robust, and controllable fashion. Different from a conventional trial-and-error approach, the reduction kinetics of a colloidal synthesis has recently been demonstrated as a reliable knob for controlling the synthesis of noble-metal nanocrystals in a deterministic and predictable manner. Here we present a brief Viewpoint on the recent progress in leveraging reduction kinetics for controlling and predicting the outcome of a synthesis of noble-metal nanocrystals. With a focus on Pd nanocrystals, we first offer a discussion on the correlation between the initial reduction rate and the internal structure of the resultant seeds. The kinetic approaches for controlling both nucleation and growth in a one-pot setting are then introduced with an emphasis on manipulation of the reduction pathways taken by the precursor. We then illustrate how to extend the strategy into a bimetallic system for the preparation of nanocrystals with different shapes and elemental distributions. Finally, the influence of speciation of the precursor on reduction kinetics is highlighted, followed by our perspectives on the challenges and future endeavors in achieving a controllable and predictable synthesis of noble-metal nanocrystals.

One-Dimensional Metal Nanostructures: From Colloidal Syntheses to Applications.

This Review offers a comprehensive review of the colloidal synthesis, mechanistic understanding, physicochemical properties, and applications of one-dimensional (1D) metal nanostructures. After a brief introduction to the different types of 1D nanostructures, we discuss major concepts and methods typically involved in a colloidal synthesis of 1D metal nanostructures, as well as the current mechanistic understanding of how the nanostructures are formed. We then highlight how experimental studies and computational simulations have expanded our knowledge of how and why 1D metal nanostructures grow. Following specific examples of syntheses for monometallic, multimetallic, and heterostructured systems, we showcase how the unique structure-property relationships of 1D metal nanostructures have enabled a broad spectrum of applications, including sensing, imaging, plasmonics, photonics, display, thermal management, and catalysis. Throughout our discussion, we also offer perspectives with regard to the future directions of development for this class of nanomaterials.

Janus Nanocages of Platinum-Group Metals and Their Use as Effective Dual-Electrocatalysts.

Janus nanocages with distinctive platinum-group metals on the outer and inner surfaces can naturally catalyze at least two different reactions. Here we report a general method based on successive deposition and then selective etching for the facile synthesis of such nanocages. We have fabricated 11 different types of Janus nanocages characterized by a uniform size and well-defined {100} facets, together with porous, ultrathin, asymmetric walls up to 1.6 nm thick. When tested as dual-electrocatalysts toward oxygen reduction and evolution reactions, the Janus nanocages based on Pt and Ir exhibited superior activities depending on the thickness and relative position of the metal layer. Density functional theory studies suggest that the alloy composition and surface structure of the nanocages both play important roles in enhancing the electrocatalytic activities by modulating the stability of key reaction intermediates.

Maximizing the Catalytic Performance of Pd@Aux Pd1-x Nanocubes in H2 O2 Production by Reducing Shell Thickness to Increase Compositional Stability.

We report a simple route based upon seed-mediated growth to the synthesis of Pd@Aux Pd1-x (0.8≤x≤1) core-shell nanocubes. Benefiting from the well-defined {100} facets and an optimal Au/Pd ratio for the surface, the nanocubes bearing a shell made of Au0.95 Pd0.05 work as an efficient electrocatalyst toward H2 O2 production, with high selectivity of 93-100 % in the low-overpotential region of 0.4-0.7 V. When the Au0.95 Pd0.05 alloy is confined to a shell of only three atomic layers in thickness, the electrocatalyst is able to maintain its surface structure and elemental composition, endowing continuous and stable production of H2 O2 during oxygen reduction at a high rate of 1.62 mol g(Pd+Au) -1  h-1 . This work demonstrates a versatile route to the rational development of active and durable electrocatalysts based upon alloy nanocrystals.

Controlling the Surface Oxidation of Cu Nanowires Improves Their Catalytic Selectivity and Stability toward C2+ Products in CO2 Reduction.

Copper nanostructures are promising catalysts for the electrochemical reduction of CO2 because of their unique ability to produce a large proportion of multi-carbon products. Despite great progress, the selectivity and stability of such catalysts still need to be substantially improved. Here, we demonstrate that controlling the surface oxidation of Cu nanowires (CuNWs) can greatly improve their C2+ selectivity and stability. Specifically, we achieve a faradaic efficiency as high as 57.7 and 52.0 % for ethylene when the CuNWs are oxidized by the O2 from air and aqueous H2 O2 , respectively, and both of them show hydrogen selectivity below 12 %. The high yields of C2+ products can be mainly attributed to the increase in surface roughness and the generation of defects and cavities during the electrochemical reduction of the oxide layer. Our results also indicate that the formation of a relatively thick, smooth oxide sheath can improve the catalytic stability by mitigating the fragmentation issue.

A Mechanistic Study of the Multiple Roles of Oleic Acid in the Oil-Phase Synthesis of Pt Nanocrystals.

Oleic acid (OAc) is commonly used as a surfactant and/or solvent for the oil-phase synthesis of metal nanocrystals but its explicit roles are yet to be resolved. Here, we report a systematic study of this problem by focusing on a synthesis that simply involves heating of Pt(acac)2 in OAc for the generation of Pt nanocrystals. When heated at 80 °C, the ligand exchange between Pt(acac)2 and OAc leads to the formation of a PtII -oleate complex that serves as the actual precursor to Pt atoms. Upon increasing the temperature to 120 °C, the decarbonylation of OAc produces CO, which can act as a reducing agent for the generation of Pt atoms and thus formation of nuclei. Afterwards, several catalytic reactions can take place on the surface of the Pt nuclei to produce more CO, which also serves as a capping agent for the formation of Pt nanocrystals enclosed by {100} facets. The emergence of Pt nanocrystals further promotes the autocatalytic surface reduction of PtII precursor to enable the continuation of growth. This work not only elucidates the critical roles of OAc at different stages in a synthesis of Pt nanocrystals, but also represents a pivotal step forward toward the rational synthesis of metal nanocrystals.

General Approach to the Synthesis of Heterodimers of Metal Nanoparticles through Site-Selected Protection and Growth.

Heterodimers of metal nanoparticles are widely sought for applications in photonics, sensing, and catalysis. In this work, we demonstrate a general approach to the fabrication of heterodimers of metal nanoparticles by leveraging the concept of site-selected growth under the protection of an inert material. When styrene is polymerized in the presence of Au nanoparticles, the resultant polystyrene (PS) can be controlled to grow from only one portion of the surface of a nanoparticle. Free of PS, the remaining portion can serve as an active site for the heterogeneous nucleation and growth of the second metal. After dissolving the PS component, we obtain heterodimers of metal nanoparticles with tunable elemental compositions and controllable physical dimensions. The contact area between the two metals can also be maneuvered by adjusting the concentration of divinylbenzene used for copolymerization with styrene. Using this method, we have prepared Au-Ag, Au-Pd, and Au-Pt heterodimers and further investigated their plasmonic properties. The capability of this approach should be extendible to the fabrication of heterodimers with a broader range of compositions and properties.

Catalytic System Based on Sub-2 nm Pt Particles and Its Extraordinary Activity and Durability for Oxygen Reduction.

Carbon-supported Pt nanoparticles are used as catalysts for a variety of reactions including the oxygen reduction reaction (ORR) key to proton-exchange membrane fuel cells, but their catalytic performance has long been plagued by detachment and sintering. Here we report the in situ growth of sub-2 nm Pt particles on a commercial carbon support via the galvanic reaction between a Pt(II) precursor and a uniform film of amorphous Se predeposited on the support. The residual Se could serve as a linker to strongly anchor the Pt nanoparticles to the carbon surface, leading to a catalytic system with extraordinary activity and durability toward ORR. Even after 20 000 cycles of accelerated durability test, the sub-2 nm Pt particles were still dispersed well on the carbon support and maintained a mass activity more than three-times as high as the pristine value of a commercial Pt/C catalyst.